Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate.
Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate.
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DOI：
10.1021/acscatal.0c02957
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发表时间：
2020-09-18
期刊：
影响因子：
12.9
通讯作者：
Phipps RJ
中科院分区：
文献类型：
--
作者：
Fanourakis A;Docherty PJ;Chuentragool P;Phipps RJ
对映体选择性过渡金属催化是当代合成研究的前沿领域。能够有效地合成对映体化合物的工艺的发展，对于在中心科学的许多不同领域工作的化学家来说，无疑是重要的。解决这一挑战的传统方法通常依赖于利用手性配体和底物之间的排斥空间相互作用来提高其中一个非对映异构体过渡态的能量。相反，本综述考察了另一种策略，在该策略中，使用了一组在过渡金属配体和底物之间进行的吸引人的非共价相互作用来控制对映体的选择性。给出并讨论了这种创造性方法成功地应用于使基本合成过程具有对映选择性的实例。在所研究的许多情况下，配体支架经过精心设计以适应这些有吸引力的相互作用，而在其他情况下，关键相互作用的重要性只在随后的计算和机制研究中得到阐明。通过对最近涉及广泛反应类的报告的探索和讨论，我们希望激励合成化学家继续基于这一强大的概念开发不对称转化。
Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development of processes that enable the efficient synthesis of enantiopure compounds is of unquestionable importance to chemists working within the many diverse fields of the central science. Traditional approaches to solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order to raise the energy of one of the diastereomeric transition states over the other. By contrast, this Review examines an alternative tactic in which a set of attractive noncovalent interactions operating between transition metal ligands and substrates are used to control enantioselectivity. Examples where this creative approach has been successfully applied to render fundamental synthetic processes enantioselective are presented and discussed. In many of the cases examined, the ligand scaffold has been carefully designed to accommodate these attractive interactions, while in others, the importance of the critical interactions was only elucidated in subsequent computational and mechanistic studies. Through an exploration and discussion of recent reports encompassing a wide range of reaction classes, we hope to inspire synthetic chemists to continue to develop asymmetric transformations based on this powerful concept.
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